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EP1270704A1 - Procédé d'extraction de composés de soufre de flux d'hydrocarbures - Google Patents

Procédé d'extraction de composés de soufre de flux d'hydrocarbures Download PDF

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Publication number
EP1270704A1
EP1270704A1 EP01115343A EP01115343A EP1270704A1 EP 1270704 A1 EP1270704 A1 EP 1270704A1 EP 01115343 A EP01115343 A EP 01115343A EP 01115343 A EP01115343 A EP 01115343A EP 1270704 A1 EP1270704 A1 EP 1270704A1
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EP
European Patent Office
Prior art keywords
stream
basic
hydrocarbon
mercaptans
disulfides
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP01115343A
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German (de)
English (en)
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EP1270704B1 (fr
Inventor
Rusty Pittman
Blaise J. Arena
Albert J. Janssen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Paques Bio Systems BV
Honeywell UOP LLC
Original Assignee
Paques Bio Systems BV
UOP LLC
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Publication date
Application filed by Paques Bio Systems BV, UOP LLC filed Critical Paques Bio Systems BV
Priority to EP01115343A priority Critical patent/EP1270704B1/fr
Priority to AT01115343T priority patent/ATE340837T1/de
Priority to DE60123404T priority patent/DE60123404D1/de
Publication of EP1270704A1 publication Critical patent/EP1270704A1/fr
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Publication of EP1270704B1 publication Critical patent/EP1270704B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/08—Recovery of used refining agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/12—Liquefied petroleum gas

Definitions

  • This invention relates to a process for removing sulfur compounds such as H 2 S and mercaptans from a hydrocarbon stream.
  • the process involves contacting the hydrocarbon stream with a weakly basic aqueous stream such as a sodium bicarbonate solution in order to extract the H 2 S and mercaptans from the hydrocarbon stream.
  • the basic stream is now flowed to a reactor containing microorganisms and oxygen in order to convert the H 2 S to sulfur and the mercaptans to disulfides.
  • the sulfur and disulfides are separated from the basic stream which can then be recycled and used to treat a fresh hydrocarbon stream.
  • Hydrocarbon streams which contain sulfur compounds such as mercaptans are usually referred to as sour hydrocarbon streams.
  • sour hydrocarbon streams In order to render these hydrocarbon streams usable, it is common in the oil refining industry to treat these streams in one of two ways.
  • One way is to contact the sour stream (usually a liquid stream) with an oxidation catalyst and an alkaline agent in the presence of an oxidizing agent such as air at reaction conditions in order to convert the mercaptans to disulfides.
  • Another way to treat these sour hydrocarbon streams is to contact the hydrocarbon stream with a strongly basic solution in order to extract the mercaptans into the basic solution thereby forming mercaptides and then taking the basic solution and regenerating it by contacting it with an oxidizing catalyst, an alkaline agent, and an oxidizing agent such as air to convert the mercaptides to disulfides.
  • the disulfides are separated from the basic solution which is recycled and used to extract more mercaptans from a fresh hydrocarbon stream.
  • the first type of process is disclosed in a number of U.S. patents, including U.S. Pat. Nos. 3,108,081; 4,156,641; 4,913,802; 4,290,913 and 4,337,147. Processes in which the mercaptans are extracted with an alkaline solution are disclosed in U.S. Patent Nos. 2,853,432; 2,921,020; 2,988,500 and 3,408,287.
  • U.S.-A-4,666,689 again discloses contacting hydrocarbon streams with alkaline solutions such as aqueous sodium hydroxide solutions.
  • alkaline solutions such as aqueous sodium hydroxide solutions.
  • sulfur compounds such as H 2 S are removed from a gaseous effluent. The gaseous waste stream is first contacted with a basic aqueous solution and then the aqueous solution is treated in a bioreactor thereby converting the H 2 S to elemental sulfur in order to regenerate the basic solution. It is disclosed in the '545 patent that an improvement in H 2 S removal is observed when the recirculating basic solution contains from 0.1 to 50 g/l of sulfur.
  • Applicants have developed a process whereby a liquid hydrocarbon stream containing both H 2 S and mercaptans is contacted with a weakly basic solution, e.g., bicarbonate solution, to simultaneously remove H 2 S and mercaptans.
  • a weakly basic solution e.g., bicarbonate solution
  • the basic solution which now contains H 2 S and mercaptans is treated in a bioreactor where the solution is contacted with a sulfide oxidizing bacteria in the presence of oxygen.
  • the H 2 S is converted to elemental sulfur while the mercaptans are converted to disulfides.
  • the oxygen level in the reactor is controlled in order to obtain these final products.
  • the sulfur and disulfides are removed from the aqueous stream which is then recirculated and used to further extract hydrogen sulfide and mercaptans from a fresh liquid hydrocarbon stream.
  • the treated liquid hydrocarbon stream now contains substantially less hydrogen sulfide and mercaptans, and can be used in various applications.
  • the present invention relates to a process for simultaneously removing H 2 S and mercaptans from a liquid hydrocarbon stream. Accordingly, one embodiment of the invention is a process comprising:
  • the sulfur is separated in a first separation zone and the disulfides are separated in a second separation zone.
  • the basic stream which enters the reactor may also contain some hydrocarbons.
  • the Figure is a simplified process flow diagram of one embodiment of the invention showing the extraction of H 2 S and mercaptans from a hydrocarbon stream with a weakly basic aqueous stream and the subsequent purification of the aqueous stream.
  • the hydrocarbon streams which can be treated by the process of this invention can vary widely and usually contain from 2 to 30 carbon atoms and include both liquid and gaseous streams. Specific examples include what is commonly referred to as liquefied petroleum gas (LPG) which contains mostly C 3 to C 4 hydrocarbons. Other examples include gasoline hydrocarbon streams, naphtha hydrocarbon streams, diesel hydrocarbon streams and streams containing mainly single components such as ethylene or pentanes (C 5 ). Usually these hydrocarbon streams will contain from 5 to about 5,000 ppm H 2 S and from 5 to 5,000 ppm mercaptans.
  • LPG liquefied petroleum gas
  • a weakly basic stream is meant a stream which contains a compound which is weakly dissociated in water (as defined in standard chemistry texts). These compounds include but are not limited to sodium carbonate, sodium bicarbonate, sodium phosphate, ammonium hydroxide, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium phosphate, etc. Strongly basic, i.e., completely dissociated compounds, such as sodium hydroxide, are not included in the basic compounds which are used to practice the present invention.
  • a basic stream Contacting of the hydrocarbon stream with the weakly basic aqueous stream (hereinafter referred to as a basic stream) can be done by means well known in the art, using vessels which are commonly known as extractors or extraction columns.
  • the extractor will contain a number of trays or packed beds in order to increase the contact between the two streams. These trays or beds are generally referred to as equilibrium stages and an extractor will contain from 1 to 20 equilibrium stages.
  • the two streams can be contacted either cocurrently or countercurrently.
  • the extraction conditions which are used in such extractors include a temperature of 20°C to 50°C, a basic compound to hydrocarbon weight ratio of 30:1 to 0.01:1, and a pressure of 100 to 2500 kPa. It should be pointed out that the strength of the basic stream can be much stronger in the extraction part of the process and then can be diluted with water to a pH of 7.1 to 10.5, which is compatible with the microorganisms in the subsequent part of the process.
  • the purified hydrocarbon stream is now separated from the basic stream and collected.
  • the hydrocarbon stream can optionally be flowed through an adsorbent bed, e.g., carbon bed, or other type of drying bed in order to remove any residual water and some sulfur compounds from the hydrocarbon stream.
  • an adsorbent bed e.g., carbon bed, or other type of drying bed in order to remove any residual water and some sulfur compounds from the hydrocarbon stream.
  • the purified hydrocarbon stream pass the copper strip corrosion test as defined by ASTM methods D-130, D-1838 and D-2420.
  • the copper strip test is a test which detects the presence of components in the hydrocarbon stream which may be corrosive to copper. Passing the copper strip test, i.e., minimal corrosion, provides assurance that problems will not be experienced with many of the fittings and connections that are commonly used in storage, transportation, etc., which are composed of copper or copper alloys.
  • the basic stream which now contains the hydrogen sulfide and mercaptans which have been converted to HS - and mercaptide ions respectively is flowed to a reactor which contains microorganisms such as cultures of the genera Thiobacillus and Thiomicrospira. These microorganisms are described in U.S. Patent 5,354,545, which is incorporated by reference. These bacteria are capable of oxidizing sulfide to elemental sulfur in the presence of oxygen.
  • the microorganisms i.e., bacteria
  • the sulfide (HS - ) to elemental sulfur.
  • the mercaptides (RS - ) are converted to disulfides.
  • the mercaptides are converted to disulfides chemically, i.e., without the aid of the bacteria.
  • the partial oxidation of the mercaptides to disulfides by the bacteria may be taking place to some extent. That is, although both biological and chemical conversion of the mercaptides to disulfides can both be occurring, it is believed that the primary conversion route is chemical.
  • the basic stream In order to carry out the conversion of hydrogen sulfide to sulfur and the mercaptans to disulfides, the basic stream must be contacted with the microorganisms and oxygen for a sufficient time.
  • the amount of oxygen fed to the reactor is controlled in order to convert the sulfide ions to elemental sulfur and the mercaptides to disulfides.
  • this amount of oxygen which can be derived from air or some other oxygen source, varies from 0.4 to 2.0 moles O 2 /moles S (total sulfur).
  • this time can vary from 15 min. to 10 hours and preferably from 2 hrs. to 5 hrs.
  • the basic stream can be treated in a batch or continuous process, a continuous process is preferred.
  • Other sulfide and mercaptide conversion conditions include a temperature of 20°C to 50°C, a pH of 7.1 to 10.5 and atmospheric pressure (or higher, e.g., 100 to 1,000 kPa).
  • hydrocarbons may be present in the basic stream. This is the result of either incomplete separation or the partial solubility of hydrocarbons in the basic stream.
  • the amount of hydrocarbons will be small and usually in the range of 1 ppm to 500 ppm by weight. It is surprising that the bacteria can function in the presence of hydrocarbons.
  • the basic stream is further processed in order to remove the sulfur and disulfide components in the basic stream. Since the disulfides are not very water soluble, if a sufficient quantity of disulfides is present, a disulfide layer will form at the top of the basic stream or solution. This disulfide layer can be withdrawn by any means known in the art.
  • the basic stream is flowed from the reactor to a first separation zone where the elemental sulfur is separated from the aqueous stream usually by filtration or any other method of separating a solid from a liquid, which methods are well known in the art.
  • the disulfides are not separated from the basic stream in the reactor.
  • concentration of the disulfides is such that only droplets are formed, then they are dispersed throughout the aqueous stream and cannot be siphoned or withdrawn from the aqueous phase.
  • the effluent from the first separation zone is flowed to a second separation zone where the disulfide oil is separated from the aqueous stream. This can be done by settling or extraction with a solvent, both of which are well known in the art.
  • the purified stream Since a portion of the purified basic stream can be recycled to the extraction step and contacted with a fresh hydrocarbon stream, it is necessary that the purified stream contain less than 0.08 g/l of elemental sulfur. Controlling the sulfur level to this amount will assure that the purified hydrocarbon stream will meet the copper strip corrosion test.
  • a hydrocarbon stream containing H 2 S and mercaptan impurities is flowed via line 1 into extraction column 2 where it is contacted with a basic stream which is flowed into column 2 via line 3 .
  • H 2 S and mercaptans are extracted from the hydrocarbon stream into the basic stream.
  • the purified hydrocarbon stream is removed via line 4 and collected.
  • the hydrocarbon stream can be removed via line 5 , flowed to adsorbent bed 6 in order to remove any water impurities and some of the residual sulfur compounds and then withdrawn and collected via line 7 .
  • the aqueous stream is removed from extraction column 2 via line 8 and flowed to reactor 9 where it is contacted with a sulfide oxidizing microorganism in the presence of oxygen, thereby converting the H 2 S to sulfur and the mercaptans to disulfides. If the disulfide oil forms a layer on top of the aqueous phase, it is withdrawn via line 10 .
  • the aqueous stream is flowed from reactor 9 via line 11 to a first separation zone 12 where the elemental sulfur is separated from the aqueous stream.
  • the sulfur is removed via line 13 and the aqueous stream is removed via line 14 .
  • a portion or all of the aqueous stream can be recycled via line 15 to extraction column 2 .
  • the aqueous stream is removed via line 16 to a second separation zone 17 where the disulfides are separated from the aqueous stream by settling, extraction or other known means.
  • the disulfides are now removed via line 18 and the aqueous stream is removed via line 19 . Again, a portion of the aqueous stream can be recycled to extraction column 2 via line 20 .
  • a LPG feed stream containing 900 ppm H 2 S and 200 ppm mercaptans was contacted with a sodium bicarbonate solution in a single stage extractor column operated at ambient temperature (24°C), an LPG feed rate of 375g/hr, a bicarbonate solution feed rate of 1080g/hr, a pressure of 1034 kPa (150 psi) and a bicarbonate solution to hydrocarbon weight ratio of 2.8.
  • the aqueous stream was separated from the hydrocarbon stream. Analysis of the hydrocarbon stream showed that 100% of the H 2 S and 60% of the mercaptans were extracted from the hydrocarbon stream.
  • the aqueous stream was flowed to a bioreactor containing Thiobacillus bacteria.
  • This reactor was operated at ambient temperature (24°C), a pH of 9.0 and an O 2 /S mole ratio range of 0.5:1 to 1.0:1.0.
  • the effluent from this bioreactor was analyzed and showed that all the H 2 S was converted with a selectivity of 75% to sulfur, a selectivity of 20% to sulfate and a selectivity of 5% to thiosulfate. Greater than 85% of the mercaptans were converted with a selectivity of 75% to disulfides.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP01115343A 2001-06-26 2001-06-26 Procédé d'extraction de composés de soufre de flux d'hydrocarbures Expired - Lifetime EP1270704B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP01115343A EP1270704B1 (fr) 2001-06-26 2001-06-26 Procédé d'extraction de composés de soufre de flux d'hydrocarbures
AT01115343T ATE340837T1 (de) 2001-06-26 2001-06-26 Verfahren zur entfernung von schwefelverbindungen aus kohlenwasserstoffbeschickungen
DE60123404T DE60123404D1 (de) 2001-06-26 2001-06-26 Verfahren zur Entfernung von Schwefelverbindungen aus Kohlenwasserstoffbeschickungen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP01115343A EP1270704B1 (fr) 2001-06-26 2001-06-26 Procédé d'extraction de composés de soufre de flux d'hydrocarbures

Publications (2)

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EP1270704A1 true EP1270704A1 (fr) 2003-01-02
EP1270704B1 EP1270704B1 (fr) 2006-09-27

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EP01115343A Expired - Lifetime EP1270704B1 (fr) 2001-06-26 2001-06-26 Procédé d'extraction de composés de soufre de flux d'hydrocarbures

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EP (1) EP1270704B1 (fr)
AT (1) ATE340837T1 (fr)
DE (1) DE60123404D1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2875236A1 (fr) * 2004-09-10 2006-03-17 Total Sa Procede et installation pour le traitement de dso
GB2485824A (en) * 2010-11-25 2012-05-30 Univ Belfast Process for removing naphthenic acids from crude oil and crude oil distillates
EP3034157A1 (fr) * 2015-02-19 2016-06-22 Paqell B.V. Procédé de traitement d'un sulfure d'hydrogène et mercaptans comprenant du gaz

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB912926A (en) * 1959-04-24 1962-12-12 Universal Oil Prod Co Process for purifying phenolic acid oils
RU2120464C1 (ru) * 1997-09-12 1998-10-20 Всероссийский научно-исследовательский институт углеводородного сырья Способ дезодорирующей очистки нефти и газоконденсата от сероводорода и низкомолекулярных меркаптанов и установка для его осуществления
US6224750B1 (en) * 1998-11-02 2001-05-01 Uop Llc Producing low sulfur hydrocarbons with biologically regenerated caustic
US6306288B1 (en) * 1998-04-17 2001-10-23 Uop Llc Process for removing sulfur compounds from hydrocarbon streams

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB912926A (en) * 1959-04-24 1962-12-12 Universal Oil Prod Co Process for purifying phenolic acid oils
RU2120464C1 (ru) * 1997-09-12 1998-10-20 Всероссийский научно-исследовательский институт углеводородного сырья Способ дезодорирующей очистки нефти и газоконденсата от сероводорода и низкомолекулярных меркаптанов и установка для его осуществления
US6306288B1 (en) * 1998-04-17 2001-10-23 Uop Llc Process for removing sulfur compounds from hydrocarbon streams
US6224750B1 (en) * 1998-11-02 2001-05-01 Uop Llc Producing low sulfur hydrocarbons with biologically regenerated caustic

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 200011, Derwent World Patents Index; Class H01, AN 2000-125489, XP002183465 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2875236A1 (fr) * 2004-09-10 2006-03-17 Total Sa Procede et installation pour le traitement de dso
GB2485824A (en) * 2010-11-25 2012-05-30 Univ Belfast Process for removing naphthenic acids from crude oil and crude oil distillates
GB2485824B (en) * 2010-11-25 2017-12-20 The Queen's Univ Of Belfast Process for removing organic acids from crude oil and crude oil distillates
EP3034157A1 (fr) * 2015-02-19 2016-06-22 Paqell B.V. Procédé de traitement d'un sulfure d'hydrogène et mercaptans comprenant du gaz
WO2016131930A1 (fr) * 2015-02-19 2016-08-25 Paqell B.V. Procédé de traitement d'un gaz comprenant du sulfure d'hydrogène et des mercaptans
CN107466249A (zh) * 2015-02-19 2017-12-12 帕奎勒有限责任公司 处理包含硫化氢和硫醇的气体的方法
US10543458B2 (en) 2015-02-19 2020-01-28 Paqell B.V. Process for treating a hydrogen sulphide and mercaptans comprising gas
CN107466249B (zh) * 2015-02-19 2020-09-15 帕奎勒有限责任公司 处理包含硫化氢和硫醇的气体的方法

Also Published As

Publication number Publication date
ATE340837T1 (de) 2006-10-15
DE60123404D1 (de) 2006-11-09
EP1270704B1 (fr) 2006-09-27

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